Hydrotreating using bulk multimetallic catalysts

ABSTRACT

A hydroprocessing process, comprising:contacting a feedstock, at hydrotreating conditions, with a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10 to form a hydrotreated product.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. Ser. No. 09/231,156, now U.S.Pat. No. 6,162,350 which was filed on Jan. 15, 1999, which is acontinuation-in-part of U.S. Ser. No. 08/900,389 now U.S. Pat. No.6,156,695 which was filed on Jul. 15, 1997.

FIELD OF THE INVENTION

This invention relates to the hydrotreating, preferablyhydrodesulfurization, hydrodenitrogenation, and combinations thereof,using a bulk multimetallic catalyst comprised of at least one Group VIIInon-noble metal and at least two Group VIB metal wherein the ratio ofGroup VIB metal to Group VIII metal is from about 10:1 to 1:10.

BACKGROUND OF THE INVENTION

As the supply of low sulfur, low nitrogen crudes decrease, refineriesare processing crudes with greater sulfur and nitrogen contents at thesame time that environmental regulations are mandating lower levels ofthese heteroatoms in products. Consequently, a need exists forincreasingly efficient desulfurtion and denitrogenation catalysts.

A family of compounds related to hydrotalcites, e.g., ammonium nickelmolybdate, has been prepared as an approach to improved hydrotreatingcatalysts. Whereas X-ray diffraction analysis has shown thathydrotalcites are composed of layered phases with positively chargedsheets and exchangeable anions located in the galleries between thesheets, the related ammonium nickel molybdate phase has molybdate anionsin interlayer galleries bonded to nickel oxyhydroxide sheets. See, forexample, Levin, D., Soled, S. L., and Ying, J. Y., Crystal Structure ofan Ammonium Nickel Molybdate prepared by Chemical Precipitation,Inorganic Chemi , Vol. 35, No. 14, p. 4191-4197 (1996). The preparationof such materials also has been reported by Teichner and Astier, Appl.Catal. 72, 321-29 (1991); Ann. Chim. Fr. 12, 33743 (1987), and C. R.Acad. Sci. 304 (II), #11, 563-6 (1987) and Mazocchia, Solid StateIonics, 63-65 (1993) 731-35.

Consequently, a need exists for increasingly efficient desulfurinzationand denitrogenation catalysts.

SUMMARY OF THE INVENTION

In accordance with this invention there is provided a process forhydrotreating raw virgin petroleum distillates, which process comprisescontacting a feedstock comprised of at least about 50 wt. % raw virgindistillate, at hydrotrating conditions, with a bulk multimetalliccatalyst comprised of at least one Group VIII non-noble metal and atleast two Group VIB metals and wherein the ratio of Group VIB metal toGroup VIII non-noble metal is from about 10:1 to about 1:10.

In a preferred embodiment of the present invention the Group VHInon-noble metal is selected from Ni and Co and the Group VIB metals areselected from Mo and W.

In another preferred embodiment of the present invention two Group VIBmetals are present as Mo and W and the ratio of Mo to W is about 9:1 toabout 1:9.

In yet another preferred embodiment of the present invention the bulkmultimetallic is represented by the formula:

(X)_(b)(Mo)_(c)(W)_(d)O_(z)

wherein X is one or more Group VIII non-noble metals, and the molarratio of b: (c+d) is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, morepreferably 0.75/1 to 1.25/1.

In still another preferred embodiment of the present invention the molarratio of c:d is preferably >0.01/1, more preferably >0.1/1, still morepreferably 1/10 to 10/1, still more preferably 1/3 to 3/1, mostpreferably substantially equimolar amounts of Mo and W, e.g., 2/3 to3/2; and z =[2b +6(c+d)]/2.

In another preferred embodiment of the present invention the bulkcatalyst is essentially amorphous and has a unique X-ray diffractionpattern showing crystalline peaks at d =2.53 Angstroms and d =1.70Angstroms.

In still another preferred embodiment of the present invention the GroupVIII non-noble metal is nickel.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is the X-ray diffraction pattern of a Ni—Mo_(0.5)W_(0.5)—Ocompound prepared by boiling precipitation before calcining (Curve A)and after calcining at 400° C. (Curve B). Note hat the patterns for boththe precursor and the decomposition product of the precursor are quitesimilar with the two peaks at essentially the same place. The ordinateis relative intensity; the abscissa is two theta (degrees).

FIG. 2 shows the X-ray diffxaction patterns, by CuKa radiation(λ=1.5405Å), of Ni—Mo_(l-x)—W_(x)—O precursor wherein curve A isMo_(0.9)W_(0.1), curve B is Mo_(0.7)W_(0.3), curve C is Mo_(0.5)W_(0.5),curve D is Mo_(0.3)W_(0.7), curve E is Mo_(0.1)W_(0.9), and curve F isMo_(O)W₁. The ordinate and abscissa are as described for FIG. 1.

FIG. 3 is a plot of HDS activity for the catalysts of examples 20 to 24hereof.

FIG. 4 is a plot of the HDN activity for the catalysts of examples 20and 24 hereof.

DETAILED DESCRIPTION OF THE INVENTION

The invention is based in part on the discovery that molybdenum in anickel-molybdenum oxide phase may be partially substituted by tungsten.The resulting phase is an essentially ammonia-free, substantiallyamorphous oxide which upon sulfidation provides enhanced hydroprocessingactivity relative to the unsubstituted Ni—Mo phase. The invention isalso based in part on the discovery of catalysts containing at least oneGroup VIII non-noble metal and at least two Group VIB metals, whereinthe ratio of Group VIB metal to Group VIII non-noble metal ranges fromabout 10:1 to about 1:10.

The bulk multimetallic catalyst composition used in the practice of thepresent invention can be used in virtally all hydroprocessing processesto treat a plurality of feeds under wide-ranging reaction conditionssuch as temperatures of from 200 to 450° C., hydrogen pressures of from5 to 300 bar, liquid hourly space velocities of from 0.05 to 10 h⁻¹ andhydrogen treat gas rates of from 35.6 to 1780 m³/m³(200 to 10000 SCF/B).The term “hydroprocessing” encompasses all processes in which ahydrocarbon feed is reacted with hydrogen at the temperatures andpressures noted above, and include hydrodemetallation, hydrodewaxing,hydrotreating, hydrogenation, hydrodesulfurization,hydrodenitrogenation, hydrodearomatization, hydroisomerization, andhydrocracking including selective hydrocracking. Depending on the typeof hydroprocessing and the reaction conditions, the products ofhydroprocessing may show improved viscosities, viscosity indices,saturates content, low temperature properties, volatilities anddepolarization. It is to be understood that hydroprocessing of thepresent invention can be practiced in one or more reaction zones and canbe practiced in either countercurrent flow or cocurrent flow mode. Bycountercurrent flow mode we mean a process mode wherein the feedstreamflows countercurrent to the flow of hydrogen-containing treat gas. Thehydroprocessing reactor can also be operated in any suitablecatalyst-bed arrangement mode. For example, it can be a fixed bed,slurry bed, or ebulating bed.

The hydrocarbon feedstocks which are typically subjected tohydrotreating herein will typically boil at a temperature above 150° C.The feedstocks can contain a substantial amount of nitrogen, e.g. atleast 10 wppm nitrogen, and even greater than 500 wppm, in the form oforganic nitrogen compounds. The feeds can also have a significant sulfurcontent, ranging from about 0.1 wt. % to 3 wt. %, or higher. If desired,the feeds can be treated in a known or conventional manner to reduce thesulfur and/or nitrogen content thereof.

Feedstocks of interest to the present invention are those that arecomprised of at least about 50 wt. % of the distillate boiling rangeproduct from atmospheric distillation unit. Preferably the feedstockcontains at least about 50 wt. % raw virgin petroleum distillate. Theremainder of the feedstock, other than the atmospheric distillationproduct can be cracked distillate feedstock. Such cracked feedstock aretypically product streams from a coker or fluid catalytic cracker.Streams from an atmospheric distillation unit are raw virgin streams inthat they have not undergone any further processing and typically have atotal sulfur content of about 0.5-2 wt. % and total nitrogen content upto about 500 wppm.

This invention is operable over a range of conditions consistent withthe intended objectives in terms of product quality improvement andconsistent with any downstream process with which this invention iscombined in either a common or sequential reactor assembly. It isunderstood that hydrogen is an essential component of the process. Thisinvention is commonly operated at a temperature of 500-800°F.(260-426.6° C.), preferably 575-700° F. (301.6-371.1° C.). Operatingpressure includes 100-1000 psig, preferably 200-800 psig, and morepreferably 300-500 psig at gas rates of 500-10,000 SCF/B, preferably750-5000 SCF/B. The feed rate may be varied over the range 0.1-100 LSHV,preferably 0.3-5 LSHV.

The hydrotreating catalyst used in the practice of the present inventionis a bulk multimetallic catalyst comprised of at least one Group VIIInon-noble metal and at least two Group VIB metals and wherein the ratioof Group VIB metal to Group VIII non-noble metal is from about 10:1 toabout 1:10. It is preferred that the catalyst be a bulk trimetalliccatalyst comprised of one Group VIII non-noble metal, preferably Ni orCo and the two Group VIB metals Mo and W. It is preferred that the ratioof Mo to W be about 9:1 to about 1:9.

The preferred bulk trimetallic catalyst compositions used in thepractice of the present invention is represented by the formula:

(X)_(b)(Mo)_(c)(W)_(d)O_(z)

wherein X is a Group VIII non-noble metal, the molar ratio of b: (c+d)is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, more preferably 0.75/1 to1.25/1;

The molar ratio of c:d is preferably >0.01/1, more preferably >0.1/1,still more preferably 1/10 to 10/1, still more preferably 1/3 to 3/1,most preferably substantially equimolar amounts of Mo and W, e.g. 2/3 to3/2; and z =[2b +6 (c+d)]/2.

The essentially amorphous material has a unique X-ray diffaction patternshowing crystalline peaks at d=2.53 Angstroms and d=1.70 Angstroms.

The mixed metal oxide is readily produced by the decomposition of aprecursor having the formula:

(NH₄)_(a)(X)_(b)(Mo)_(c)(W)_(d)O_(z)

wherein the molar ratio of a:b is <1.0/1, preferably 0-1: and b. c, andd. are as defined above, and z =[a+2b+6(c+d)]/2. The precursor hassimilar peaks at d =2.53 and 1.70 Angstroms.

Decomposition of the precursor may be eftected at elevated temperatures,e.g., temperatures of at least about 300° C., preferably about 300-450°C., in a suitable atmosphere. e.g., inerts such as nitrogen, argon, orsteam, until decomposition is substantially complete. i.e., the ammoniumis substantially completely driven off. Substantially completedecomposition can be readily established by thermogravimetric analysis(TGA), i.e. flattening of the weight change curve.

The catalyst compositions used in the practice of the present inventioncan be prepared by any suitable means. One such means is a methodwherein not all of the metals are in solution. Generally, the contactingof the metal components in the presence of the protic liquid comprisesmixing the metal component and subsequently reacting the resultingmixture. It is essential to the solid route that at least one metalcomponents is added at least partly in the solid state during the mixingstep and that the metal of at least one of the metal components whichhave been added at least partly in the solid state remains at leastpartly in the solid state during the mixing and reaction step. “Metal”in this context does not mean the metal in its metallic form but presentin a metal compound, such as the metal component as initially applied oras present in the bulk catalyst composition.

Generally, during the mixing step either at least one metal component isadded at least partly in the solid state and at least one metalcomponent is added in the solute state, or all metal components areadded at least partly in the solid state, wherein at least one of themetals of the metal components which are added at least partly in thesolid state remains at least partly in the solid state during the entireprocess of the solid route. That a metal component is added “in thesolute state” means that the whole amount of this metal component isadded as a solution of this metal component in the protic liquid. That ametal component is added “at least partly in the solid state” means thatat least part of the metal component is added as solid metal componentand, optionally, another part of the metal component is added as asolution of this metal component in the protic liquid. A typical exampleis a suspension of a metal component in a protic liquid in which themetal is at least partly present as a solid, and optionally partlydissolved in the protic liquid.

To obtain a bulk catalyst composition with high catalytic activity, itis therefore preferred that the metal components, which are at leastpartly in the solid state during contacting, are porous metalcomponents. It is desired that the total pore volume and pore sizedistribution of these metal components is approximately the same asthose of conventional hydrotreating catalysts. Conventionalhydrotreating catalysts generally have a pore volume of 0.05-5 ml/g,preferably of 0.1-4 ml/g, more preferably of 0.1-3 ml/g and mostpreferably of 0.1-2 ml/g determined by nitrogen adsorption. Pores with adiameter smaller than 1 nm are generally not present in conventionalhydrotreating catalysts. Further, conventional hydrotreating catalystshave generally a surface area of at least 10 m²/g and more preferably ofat least 50 m²/g and most preferably of at least 100 m²/g, determinedvia the B.E.T. method. For instance, nickel carbonate can be chosenwhich has a total pore volume of 0.19-0.39 ml/g and preferably ot0.24-0.35 ml/g determined by nitrogen adsorption and a surface area of150-400 m²/g and more preferably of 200-370 m²/g determined by theB.E.T. method. Furthermore these metal components should have a medianparticle diameter of at least 50 nm, more preferably at least 100 nm,and preferably not more than 5000 nm and more preferably not more than3000 nm. Even more preferably, the median particle diameter lies in therange of 0.1-50 μn and most preferably in the range of 0.5-50 μm. Forinstance, by choosing a metal component which is added at least partlyin the solid state and which has a large median particle diameter, theother metal components will only react with the outer layer of the largemetal component particle. In this case, so-called “core-shell”structured bulk catalyst particles are obtained.

An appropriate morphology and texture of the metal component can eitherbe achieved by applying suitable preformed metal components or bypreparing these metal components by the above-described precipitationunder such conditions that a suitable morphology and texture isobtained. A proper selection of appropriate precipitation conditions canbe made by routine experimentation.

As has been set out above, to retain the morphology and texture of themetal components which are added at least partly in the solid state, itis essential that the metal of the metal component at least partlyremains in the solid state during the whole process of this solid route.It is noted again that it is essential that in no case should the amountof solid metals during the process of the solid route becomes zero. Thepresence of solid metal comprising particles can easily be detected byvisual inspection at least if the diameter of the solid particles inwhich the metals are comprised is larger than the wavelength of visiblelight. Of course, methods such as quasi-elastic light scattering (QELS)or near forward scattering which are known to the skilled person canalso be used to ensure that in no point in time of the process of thesolid route, all metals are in the solute state.

The protic liquid to be applied in the solid or solution route of thisinvention for preparing catalyst can be any protic liquid. Examplesinclude water, carboxylic acids, and alcohols such as methanol orethanol. Preferably, a liquid comprising water such as mixtures of analcohol and water and more preferably water is used as protic liquid inthis solid route. Also different protic liquids can be appliedsimultaneously in the solid route. For instance, it is possible to add asuspension of a metal component in ethanol to an aqueous solution ofanother metal component.

The Group VIB metal generally comprises chromium, molybdenum, tungsten,or mixtures thereof. Suitable Group VIII non-noble metals are, e.g.,iron, cobalt, nickel, or mixtures thereof. Preferably, a combination ofmetal components comprising nickel, molybdenum and tungsten or nickel,cobalt, molybdenum and tungsten is applied in the process of the solidroute. If the protic liquid is water, suitable nickel components whichare at least partly in the solid state during contacting comprisewater-insoluble nickel components such as nickel carbonate, nickelhydroxide, nickel phosphate, nickel phosphite, nickel formate, nickelsulfide, nickel molybdate, nickel tungstate, nickel oxide, nickel alloyssuch as nickel-molybdenum alloys, Raney nickel, or mixtures thereof.Suitable molybdenum components, which are at least partly in the solidstate during contacting, comprise water-insoluble molybdenum componentssuch as molybdenum (di- and tri) oxide, molybdenum carbide, molybdenumnitride, aluminum molybdate, molybdic acid (e.g. H₂MoO₄), molybdenumsulfide, or mixtures thereof. Finally, suitable tungsten componentswhich are at least partly in the solid state during contacting comprisetungsten di- and trioxide, tungsten sulfide (WS₂ and WS₃), tungstencarbide, tungstic acid (e.g. H₂W0₄—H₂O, H₂W₄O_(13—)9H₂O), tungstennitride, aluminum tungstate (also meta-, or polytumgstate) or mixturesthereof. These components are generally commercially available or can beprepared by, e.g., precipitation. e.g., nickel carbonate can be preparedfrom a nickel chloride, sulfate, or nitrate solution by adding anappropriate amount of sodium carbonate. It is generally known to theskilled person to choose the precipitation conditions in such a way asto obtain the desired morphology and texture.

In general, metal components, which mainly contain C, O, and/or Hbesides the metal, are preferred because they are less detrimental tothe environment. Nickel carbonate is a preferred metal component to beadded at least partly in the solid state because when nickel carbonateis applied, CO₂ evolves and positively influences the pH of the reactionmixture. Further, due to the transformation of carbonate into CO₂, thecarbonate does not end up in the wastewater.

Preferred nickel components which are added in the solute state arewater-soluble nickel components, e.g. nickel nitrate, nickel sulfite,nickel acetate, nickel chloride, or mixtures thereof Preferredmolybdenum and tungsten components which are added in the solute stateare water-soluble molybdenum and tungsten components such as alkai metalor ammonium molybdate (also peroxo-, di-, tri-, tetra-, hepta-, octa-,or tetradecarnolybdate), Mo—P heteropolyanion compounds, Wo—Siheteropolyanion compounds, W—P heteropolyanion compounds, W—Siheteropolyanion compounds, Ni—Mo—W heteropolyanion compounds, Co—Mo—Wheteropolyanion compounds, alkali metal or ammonium tungstates (alsometa-, para-, hexa-, or polytungstate), or mixtures thereof.

Preferred combinations of metal components are nickel carbonate,tungstic acid and molybdenum oxide. Another preferred combination isnickel carbonate, ammonium dimolybdate and ammonium metatungstate. It iswithin the scope of the skilled person to select further suitablecombinations of metal components. It must be noted that nickel carbonatealways comprises a certain amount of hydroxy-groups. It is preferredthat the amount of hydroxy-groups present in the nickel carbonate behigh.

An alternative method of preparing the catalysts used in the practice ofthe present invention is to prepare the bulk catalyst composition by aprocess comprising reacting in a reaction mixture a Group VIII non-noblemetal component in solution and a Group VIB metal component in solutionto obtain a precipitate. As in the case of the solid route, preferably,one Group VIII non-noble metal component is reacted with two Group VIBmetal components. The molar ratio of Group VIB metals to Group VIIInon-noble metals applied in the process of the solution route ispreferably the same as described for the solid route. Suitable Group VIBand Group VIII non-noble metal components are, e.g. those water-solublenickel, molybdenum and tungsten components described above for the solidroute. Further Group VIII non-noble metal components are, e.g., cobaltor iron components. Further Group VIB metal components are. e.g.chromium components. The metal components can be added to the reactionmixture in solution, suspension or as such. If soluble salts are addedas such, they will dissolve in the reaction mixture and subsequently beprecipitated. Suitable Group VIB metal salts which are soluble in waterare ammonium salts such as ammonium dimolybdate, ammonium tri-, tetra-hepta-, octa-, and tetradeca- molybdate, ammonium para-, meta-, hexa-,and polytungstate, alkali metal salts, silicic acid salts of Group VIBmetals such as molybdic silicic acid, molybdic silicic tungstic acid,tungstic acid, metatungstic acid, pertungstic acid, heteropolyanioncompounds of Mo—P, MoSi, W—P, and W—Si. It is also possible to add GroupVIB metal-containing compounds which are not in solution at the time ofaddition, but where solution is effected in the reaction mixture.Examples of these compounds are metal compounds which contain so muchcrystal water that upon temperature increase they will dissolve in theirown metal water. Further, non-soluble metal salts may be added insuspension or as such, and solution is effected in the reaction mixture.Suitable non-soluble metals salts are heteropolyanion compounds ofCo—Mo—W (moderately soluble in cold water), heteropolyanion compounds ofNi—Mo—W (moderately soluble in cold water).

The reaction mixture is reacted to obtain a precipitate. Precipitationis effected by adding a Group VIII non-noble metal salt solution at atemperature and pH at which the Group VIII non-noble metal and the GroupVIB metal precipitate, adding a compound which complexes the metals andreleases the metals for precipitation upon temperature increase or pHchange or adding a Group VIB metal salt solution at a temperature and pHat which the Group VIII non-noble metal and Group VIB metal precipitate,changing the temperature, changing the pH, or lowering the amount of thesolvent. The precipitate obtained with this process appears to have highcatalytic activity. In contrast to the conventional hydroprocessingcatalysts, which usually comprise a carrier impregnated with Group VIIInon-noble metals and Group VIB metals, said precipitate can be usedwithout a support. Unsupported catalyst compositions are usuallyreferred to as bulk catalysts. Changing the pH can be done by addingbase or acid to the reaction mixture, or adding compounds, whichdecompose upon temperature, increase into hydroxide ions or H⁺ions thatrespectively increase or decrease the pH. Examples of compounds thatdecompose upon temperature increase and thereby Increase or decrease thepH are urea, nitrites, ammonium cyanate, ammonium hydroxide, andammonium carbonate.

In an illustrative process according to the solution route, solutions ofammonium salts of a Group VIB metal are made and a solution of a GroupVIII non-noble metal nitrate is made. Both solutions are heated to atemperature of approximately 90° C. Ammonium hydroxide is added to theGroup VIB metal solution. The Group VIII non-noble metal solution isadded to the Group VIB metal solution and direct precipitation of theGroup VIB and Group VIII non-noble metal components occurs. This processcan also be conducted at lower temperature andior decreased pressure orhigher temperature and/or increased pressure.

In another illustrative process according to the solution route, a GroupVIB metal salt, a Group VIII metal salt, and ammonium hydroxide aremixed in solution together and heated so that ammonia is driven off andthe pH is lowered to a pH at which precipitation occurs. For instancewhen nickel, molybdenum, and tungsten components are applied,precipitation typically occurs at a pH below 7.

Independently from whether the solid or solution route is chosen theresulting bulk catalyst composition preferably comprises and morepreferably consists essentially of bulk catalyst particles having thecharacteristics of the bulk catalyst particles described under theheading “Catalyst compositions of the invention.”

The bulk catalyst composition can generally be directly shaped intohydroprocessing particles. If the amount of liquid of the bulk catalystcomposition is so high that it cannot be directly subjected to a shapingstep, a solid liquid separation can be performed before shaping.Optionally the bulk catalyst composition, either as such or after solidliquid separation, can be calcined before shaping.

The median diameter of the bulk catalyst particles is at least 50 nm,more preferably at least 100 nm, and preferably not more than 5000 μmand more preferably not more than 3000 μm. Even more preferably, themedian particle diameter lies in the range of 0.1-50 μm and mostpreferably in the range of 0.5-50μm.

If a binder material is used in the preparation of the catalystcomposition it can be any material that is conventionally applied as abinder in hydroprocessing catalysts. Examples include silica,silica-alumina, such as conventional silica-alumina, silica-coatedalumina and alumina-coated silica, alumina such as (pseudo)boehmite, orgibbsite, titania, zirconia, cationic clays or anionic clays such assaponite, bentonite, kaoline, sepiolite or hydrotalcite, or mixturesthereof. Preferred binders are silica, silica-alumina, alumina, titanic,zirconia, or mixtures thereof. These binders may be applied as such orafter peptiztion. It is also possible to apply precursors of thesebinders that, during the process of the invention are converted into anyof the above-described binders. Suitable precursors are, e g., alkalimetal aluminates (to obtain an alumina binder), water glass (to obtain asilica binder), a mixture of alkali metal aluminates and water glass (toobtain a silica alumina binder), a mixture of sources of a di-, tri-,and/or tetravalent metal such as a mixture of water-soluble salts ofmagnesium, aluminum and/or silicon (to prepare a cationic clay and/oranionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.

If desired, the binder material may be composited with a Group VIB metaland/or a Group VIII non-noble metal, prior to being composited with thebulk catalyst composition and/or prior to being added during thepreparation thereof. Compositing the binder material with any of thesemetals may be carried out by impregnation of the solid binder with thesematerials. The person skilled in the art knows suitable impregnationtechniques. If the binder is peptized, it is also possible to carry outthe peptization in the presence of Group VIB and/or Group VllI non-noblemetal components.

If alumina is applied as binder, the surface area preferably lies in therange of 100-400 m²/g, and more preferably 150-350 m^(2/)g, measured bythe B.E.T. method. The pore volume of the alumina is preferably in therange of 0.5-1.5 ml/g measured by nitrogen adsorption.

Generally, the binder material to be added in the process of theinvention has less catalytic activity than the bulk catalyst compositionor no catalytic activity at all. Consequently, by adding a bindermaterial, the activity of the bulk catalyst composition may be reduced.Therefore, the amount of binder material to be added in the process ofthe invention generally depends on the desired activity of the finalcatalyst composition. Binder amounts from 0-95 wt. % of the totalcomposition can be suitable, depending on the envisaged catalyticapplication. However, to take advantage of the resulting unusual highactivity of the composition of the present invention, binder amounts tobe added are generally in the range of 0.5-75 wt. % of the totalcomposition.

The catalyst composition can be directly shaped. Shaping comprisesextrusion, pelletizing, beading, and/or spray drying. It must be notedthat if the catalyst composition is to be applied in slurry typereactors. fluidized beds, moving beds, expanded beds. or ebullatingbeds, spray drying or beading is generally applied for fixed bedapplications, generally, the catalyst composition is extruded,pelletized and/or beaded. In the latter case, prior to or during theshaping step, any additives that are conventionally used to facilitateshaping can be added. These additives may comprise aluminum stearate,surfactants, graphite or mixtures thereof. These additives can be addedat any stage prior to the shaping step. Further, when alumina is used asa binder, it may be desirable to add acids prior to the shaping stepsuch as nitric acid to increase the mechanical strength of theextrudates.

It is preferred that a binder material is added prior to the shapingstep. Further, it is preferred that the shaping step is carried out inthe presence of a liquid, such as water. Preferably, the amount ofliquid in the extrusion mixture, expressed as LOI is in the range of20-80%.

The resulting shaped catalyst composition can, after an optional dryingstep, be optionally calcined. Calcination however is not essential tothe process of the invention. If a calcination is carried out in theprocess of the invention, it can be done at a temperature of, e.g., from100°-600° C. and preferably 350° to 500° C. for a time varying from 0 5to 48 hours. The drying of the shaped particles is generally carried outat temperatures above 100° C.

In a preferred embodiment of the invention, the catalyst composition issubjected to spray drying, (flash) drying, milling, kneading, orcombinations thereof prior to shaping. These additional process stepscan be conducted either before or after a binder is added, aftersolid-liquid separation, before or after calcination and subsequent tore-wetting. It is believed that by applying any of the above-describedtechniques of spray drying, (flash) drying, milling, kneading, orcombinations thereof, the degree of mixing between the bulk catalystcomposition and the binder material is improved. This applies to bothcases where the binder material is added before or after the applicationof any of the above-described methods. However, it is generallypreferred to add the binder material prior to spray drying and/or anyalternative technique. If the binder is added subsequent to spray dryingand/or any alternative technique, the resulting composition ispreferably thoroughly mixed by any conventional technique prior toshaping. An advantage of, e.g., spray drying is that no wastewaterstreams are obtained when this technique is applied.

Furthermore, a cracking component may be added during catalystpreparation. The cracking component may serve as an isomerizationenhancer. The cracking component can be any conventional crackingcomponent such as cationic clays, anionic clays, zeolites such as ZSM-5,(ultra-stable) zeolite Y, zeolite X, ALPO's. SAPO's, amorphous crackingcomponents such as silica-alumina, or mixtures thereof. It will be clearthat some materials may act as a binder and a cracking component at thesame time. For instance, silica-alumina may have at the same time acracking and a binding function.

If desired, the cracking component may be composited with a Group VIBmetal and/or a Group VIII non-noble metal prior to being composited withthe bulk catalyst composition and/or prior to being added during thepreparation thereof. Compositing the cracking component with any ofthese metals may be carried out by impregnation of the crackingcomponent with these materials.

The cracking component, which can comprise about 0-80 wt. %. based onthe total weight of the catalyst, can be added at any stage of theprocess of the present invention prior to the shaping step. However, itis preferred to add the cracking component during the compositing step(ii) with the binder.

Generally, it depends on the envisaged catalytic application of thefinal catalyst composition which of the above-described crackingcomponents is added. A zeolite is preferably added if the resultingcomposition shall be applied in hydrocracking or fluid, catalyticcracking. Other cracking components such as silica-alumina or cationicclays are preferably added if the final catalyst composition shall beused in hydrotreating applications. The amount of cracking material thatis added depends on the desired activity of the final composition andthe application envisaged and thus may vary from 0-90 wt. %. based onthe total weight of the catalyst composition.

If desired, further materials can be added in addition to the metalcomponents already added. These materials include any material that isadded during conventional hydroprocessing catalyst preparation. Suitableexamples are phosphorus compounds, boron compounds, fluorine-containingcompounds, additional transition metals, rare earth metals, fillers, ormixtures thereof.

Suitable phosphorus compounds include ammonium phosphate, phosphoricacid, or organic phosphorus compounds. Phosphorus compounds can be addedat any stage of the process of the present invention prior to theshaping step and/or subsequent to the shaping step. If the bindermaterial is peptized, phosphorus compounds can also be used forpeptization. For instance, the binder can be peptized by contacting thebinder with phosphoric acid or with a mixture of phosphoric and nitricacid.

Suitable additional transition metals are, e.g., rhenium, ruthenium,rhodium, iridium, chromium, vanadium, iron, cobalt, platinum, palladium,cobalt, nickel, molybdenum, or tungsten, Nickel, molybdenum and tungstencan be applied in the form of any of the water-insoluble nickel,molybdenum and/or tungsten components that are described above for thesolid route. These metals can be added at any stage of the process ofthe present invention prior to the shaping step. Apart from adding thesemetals during the process of the invention, it is also possible tocomposite the final catalyst composition therewith. It is, e.g.,possible to impregnate the final catalyst composition with animpregnation solution comprising any of these metals.

The processes of the present invention for preparing the bulk catalystcompositions may further comprise a sulfidation step. Sulfidation isgenerally carried out by contacting the catalyst composition orprecursors thereof with a sulfur containing compound such as elementarysulfur, hydrogen sulfide or polysulfides. The sulfidation can generallybe carried out subsequently to the preparation of the bulk catalystcomposition but prior to the addition of a binder material, and/orsubsequently to the addition of the binder material but prior tosubjecting the catalyst composition to spray drying and/or anyalternative method, and/or subsequently to subjecting the composition tospray drying and/or any alternative method but prior to shaping, and/orsubsequently to shaping the catalyst composition. It is preferred thatthe sulfidation is not carried out prior to any process step thatreverts the obtained metal sulfides into their oxides. Such processsteps are, e.g., calcination or spray drying or any other hightemperature treatnent in the presence of oxygen. Consequently, if thecatalyst composition is subjected to spray drying and/or any alternativetechnique, the sulfidation should be carried out subsequent to theapplication of any of these methods.

Additionally to, or instead of, a sulfidation step, the bulk catalystcomposition may be prepared from at least one metal sulfide. If, e.g.the solid route is applied in step (i), the bulk catalyst component canbe prepared form nickel sulfide and/or molybdenum sulfide and/ortungsten sulfide.

If the catalyst composition is used in a fixed bed processes, thesulfidation is preferably carried out subsequent to the shaping stepand, if applied, subsequent to the last calcination step. Preferably,the sulfidation is carried out ex situ, i.e., the sulfidation is carriedout in a separate reactor prior to loading the sulfided catalystcomposition into the hydroprocessing unit. Furthermore, it is preferredthat the catalyst composition is both sulfided ex situ and in situ.

One or more of the reaction zones may contain a conventionalhydrodcsulfurization. catalyst. Suitable conventionalhydrodesulirization catalysts for use in the present invention includesthose that are comprised of at least one Group VIII metal, preferablyFe, Co or Ni, more preferably Co and/or Ni, and most preferably Co; andat least one Group VI metal, preferably Mo or W, more preferably Mo, ona relatively high surface area support materiaL preferably alumina.Other suitable hydrodesulfurization catalyst supports include zeolites,amorphous silica-alumina, and titania-alumina. Noble metal catalysts canalso be employed, preferably when the noble metal is selected from Pdand Pt. It is within the scope of the present invention that more thanone type of hydrodesulfurization catalyst be used in the same reactionvessel. The Group VIII metal is typically present in an amount rangingfrom about 2 to 20 wt. %, preferably from about 4 to 12%. The Group VImetal will typically be present in an amount ranging from about 5 to 50wt. %, preferably from about 10 to 40 wt. %, and more preferably fromabout 20 to 30 wt. %. All metal weight percents are on support By “onsupport” we mean that the percents are based on the weight of thesupport. For example, if the support were to weigh 100 g. then 20 wt. %Group VIII metal would mean that 20 g. of Group VIII metal was on thesupport.

It has been found that in this case, the bulk catalyst particles aresintering-resistant. Thus the active surface area of the bulk catalystparticles is maintained during use. The molar ratio of Group VIB toGroup VIII non-noble metals ranges generally from 10:1-1:10 andpreferably from 3:1-1:3. In the case of a core-shell structuredparticle, these ratios of course apply to the metals contained in theshell. If more than one Group VIB metal is contained in the bulkcatalyst particles, the ratio of the different Group VIB metals isgenerally not critical. The same holds when more than one Group VIIInon-noble metal is applied. In the case where molybdenum and tungstenare present as Group VIB metals, the molybenum:tungsten ratio preferablylies in the range of 9:1 -1:9. Preferably the Group VIII non-noble metalcomprises nickel and/or cobalt It is further preferred that the GroupVIB metal comprises a combination of molybdenum and tungsten.Preferably, combinations of nickel/molybdenum/tungsten andcobalt/tmolybdenum/tungsten and nickel/cobalt/molybdenum/tungsten areused. These types of precipitates appear to be sinter-resistant. Thus,the active surface area of the precipitate is retained during use. Themetals are preferably present as oxidic compounds of the correspondingmetals, or if the catalyst composition has been sulfided, sulfidiccompounds of the corresponding metals.

Preferably the particles have a surface area of at least 50 m²/g andmore preferably of at least 100 m²/g measured via the B.E.T. method. Itis furthermore preferred that the particles comprise 50-100 wt. %, andeven more preferably 70-100 wt. % of at least one Group VIII non-noblemetal and at least one Group VIB metal, based on the total weight of theparticles, calculated as metal oxides. The amount of Group VIB and GroupVIII non-noble metals can easily be determined via TEM-EDX.

It is desired that the pore size distribution of the particles isapproximately the same as the one of conventional hydrotreatingcatalysts. More in particular, these particles have preferably a porevolume of 0.05-5 ml/g, more preferably of 0.1-4 ml/g, still morepreferably of 0.1-3 ml/g and most preferably 0.1-2 ml/g determined bynitrogen adsorption. Preferably, pores smaller than 1 nm are notpresent. Furthermore these particles preferably have a median diameterof at least 50 nm, more preferably at least 100 nm, and preferably notmore than 5000 μm and more preferably not more thm 3000 μm. Even morepreferably, the median particle diameter lies in the range of 0.1-50 μmand most preferably in the range of 0 5-50 μm.

The surface area of the catalyst composition preferably is at least 40m²/g, more preferably at least 80 m²/g and most preferably at least 120m²/g. The total pore volume of the catalyst composition is preferably atleast 0.05 ml/g and more preferably at least 01 ml/g as determined bywater porosimetry. To obtain catalyst compositions with high mechanicalstrength, it may be desirable that the catalyst composition of theinvention has a low macroporosity.

It was found that the bulk catalyst particles have a characteristicX-ray diffraction pattern which differs from catalysts obtained byco-mixing and conventional hydroprocessing catalysts obtained byimpregnation. The X-ray diffraction pattern of the bulk catalystparticles comprises, and preferably essentially consists of, peakscharacteristic to the reacted metal components. If, e.g., nickelhydroxy-carbonate has been contacted with a molybdenum and tungstencomponent as described above, the resulting bulk catalyst particles arecharacterized by an X-ray diffraction pattern which comprises peaks at dvalues of (4.09 Å), 2.83 Å, 2.53 Å, 2.32 Å, 2.23 Å, 1.70 Å, (1.54 Å),1.47 Å. Values in brackets indicate that the corresponding peaks arerather broad and/or have a low intensity or are not distinguished atall. The term “the X-ray diffraction pattern essentially consists of”these peaks means that apart from these peaks, there are essentially nofurther peaks contained in the diffraction pattern. The precipitate forcatalyst obtained by the solution route has a characteristic X-raydiffraction pattern which differs from catalyst obtained by co-mixingand conventional hydroprocessing catalysts obtained by impregnation. Forinstance the X-ray diffraction pattern of a Ni—Mo—W precipitate asprepared by the solution route has peaks at d values of 2.52 Å, 1.72 Åand 1.46 Å.

Also as previously stated, the catalyst composition may compriseconventional hydroprocessing catalysts. The binder materials andcracking components of the conventional hydroprocessing catalystgenerally comprise any of the above-described binder materials andcracking components. The hydrogenation metals of the conventionalhydroprocessing catalyst generally comprise Group VIB and (iroup VIIInon-noble metals such as combinations of nickel or cobalt withmolybdenum or tungsten. Suitable conventional hydroprocessing catalystsare, e.g. hydrotreating catalysts. These catalysts can be in the spent,regenerated, or fresh state.

As will be clear from the above, it is possible to add the Group VIIInon-noble metal containing compound and the Group VIB metal-containingcompound in various ways, at various temperatures and pHs, in solution,in suspension, and as such, simultaneously and sequentially.

The precursor compound can also be readily prepared by one of severalmethods, including a variation of the boiling decomposition method usedby Teichner and Astier in which a tungsten compound is added to theinitial mixture of a molybdenum salt, a nickel salt and ammoniumhydroxide. Direct precipitation and pH controlled precipitation may alsobe used to prepare the precursor compound. In all cases, however, watersoluble salts of nickel, molybdenum and tungsten are employed.

Preferably, the molybdenum and tungsten salts are ammonium compounds,e.g., ammonium molybdate, ammonium metatungstate, while the nickel saltmay be the nitrate or hydrated nitrates.

The decomposed precursor can be sulfided or pre-sulfided by a variety ofknown methods. For example, the decomposition product can be contactedwith a gas comprising H₂S and hydrogen, e.g., 10% H₂S/H₂, at elevatedtemperatures for a period of time sufficient to sulfide thedecomposition product, usually at the point of H₂S breakthrough in theexit gas. Sulfiding can also be effected, in situ, by passing a typicalfeedstock containing sulfur over the decomposition product.

Process conditions applicable for the use of the catalysts describedherein may vary widely depending on the feedstock to be treated. Thus,as the boiling point of the feed increases, the severity of theconditions will also increase. The following table serves to illustratetypical conditions for a range of feeds.

TYPICAL SPACE BOILING VELO- RANGE TEMP. PRESS, CITY H₂ GAS RATE FEED °C. ° C. BAR V/V/HR SCF/B naphtha  25-210 100-370 10-60   0.5-10100-2,000 diesel 170-350 200-400 15-110 0.5-4 500-6,000 heavy gas325-475 260-430 15-170 0.3-2 1000-6,000  oil lube oil 290-550 200-450 6-210 0.2-5  100-10,000 residuum 10-50% > 340-450  65-1100 0.1-12,000-10,000  575

The following examples will serve to illustrate, but not limit thisinvention.

EXAMPLE 1 Preparation of NH₄—Ni—Mo—O Phase (boiling decomposition as perTeichner and Astier procedure)

In a 1 liter flask, 26.5 g ammonium molybdate (0.15 moles Mo) and 43.6 gnickel nitrate hexahydrate (0. 15 moles Ni) were dissolved in 300 cc ofwater so that the resulting pH equaled 4.3, To this solution, aconcentrated NH₄OH solution was added. At first a precipitate formedwhich on further addition of NH₄OH dissolved to give a clear bluesolution with a pH of 8.3, and additional NH₄OH (˜250cc) was added untila pH of 10 was reached. The solution was heated to 90° C. for 3 h duringwhich ammonia gas evolved and a green precipitate formed. The final pHlay between 6.8 and 7. The suspension was cooled to room temperature,filtered, washed with water and dried at 120° C. overnight About 18.6 gof material was obtained. The sample analyzed for Ni at 26.6 wt.% and Moat 34 wt.%. The X-ray diffraction spectra of the phase matches thepattern reported by Teichner.

EXAMPLE 2 Preparation of NH₄—Ni—Mo_(.5)W_(.5)—O by Boiling Decomposition

In a 1 liter flask, 13.2 g ammonium molybdate (0.075 moles Mo), 18.7 gammonium metatungstate (.075 moles W) and 43.6 g nickel nitratehexahydrate (0.15 moles Ni) were dissolved in 300cc of water so that theresulting pH equaled 4.3. To this solution, a concentrated NH₄OHsolution (˜600 cc) was added until the pH reached 10. At this point,some precipitate remained. The solution was refluxed at ˜100° C. for 3h. During this heating, the precipitate dissolved to give a clear bluesolution and on frther heating, a green precipitate formed. The heatingwas continued until the pH reached between 6.8 and 7. The suspension wascooled to room temperature, filtered, washed with water and dried at120° C. overnight. 18 grams of material is obtained. The X-raydiffraction spectra of the phase is given in FIG. 1 showing an amorphousbackground with the two largest peaks at d=2.53 and 1.70Å.

EXAMPLE 3 Preparation of NH4—Ni—Mo_(.5)W_(.5)—O by Direct Precipitation

In a 1 liter flask, 17.65 g of ammonium molybdate (0.1 mole Mo) and24.60 g of ammonium metatungstate (0.1 mole W) were dissolved in 800 ccof water giving a solution pH of ˜5.2. To this solution 0.4 moles ofNH₄OH (˜30 cc) was added, raising the pH to ˜9.8 (solution A). Thissolution was warmed to 90° C.

A second solution was prepared by adding 58.2 g of nickel nitrate, (0.2moles Ni) which was dissolved in 50 cc of water (solution B) andmaintained at 90° C. This solution was added dropwise at a rate of 7cc/min into the ammonium molybdate/ammonium metatungstate solution. Aprecipitate begins to form after ¼ of the solution was added. Thissuspension which was at a pH ˜6.5 was stirred for 30 minutes while thetemperature was maintained at 90° C. The material was filtered hot,washed with hot water, and dried at 120° C. Approximately 38 g ofmaterial was recovered.

EXAMPLE 4 Preparation of NH₄—Ni—Mo_(.5)W_(.5)—O by Controlled pHPrecipitation

Two solutions were prepared with the same amounts of nickel, tungsten,molybdenum and ammonium hydroxide are described in Example 3 (solutionsA and B) except that each solution contained about 700 cc of water. Thetwo solutions were added into a separate vessel initially containing 400cc of water held at 90° C. Solution B (the acidic solution) was pumpedinto the vessel at a constant rate of ˜15cc/min, while solution A isadded through a separate pump which is under feedback PC control and setto maintain the pH at 6.5. On mixing the two solutions a precipitateforms. The slurry was stirred at 90° C. for 30 minutes, filtered hot,washed with hot water, and dried at 120° C.

EXAMPLE 5 Catalytic Evaluation Using Dibenzothiophene (DBT)

1.5-2 g of the catalysts of Examples 1-4 were placed in a quartz boatwhich was in turn inseted into a horizontal quartz tube and placed intoa Lindberg furnace. The temperature was raised to 370° C. in about onehour with N2 flowing at 50 cc/m, and the flow continued for 1.5 h at370° C. N₂ was switched off and 10% H₂S/H₂ then added to the reactor at20 cc/m, the temperature increased to 400° C., and held there for 2hours. The heat was then shut off and the catalyst cooled in flowingH₂S/H₂ to 70° C., at which point this flow was discontinued and N₂ wasadded. At room temperature, the quartz tube was removed and the materialtransferred into a N₂ purged glove box. Catalysts were evaluated in a300cc modified Carberry batch reactor designed for constant hydrogenflow. The catalyst was pilled and sized to 20/40 mesh and one gram wasloaded into a stainless steel basket, sandwiched between a layer ofmullite beads. 100 cc of liquid feed, containing 5 wt % dibenzothiophenein decalin was added to the autoclave. A hydrogen flow of 100 cc/min waspassed through the reactor and the pressure was maintained at 3150 kPausing a back pressure regulator. The temperature was raised to 350° C.at 54 deg/min and run until either 50% DBT was converted or until 7hours was reached. A small aliquot of product was removed every 30minutes and analyzed by GC. Rate constants for the overall conversion aswell as the conversion to the reaction products biphenyl (BP) andcyclohexylbenzene (CHB) were calculated as described by M. Daage and R.R Chianelli [J. Cat. 149.414-27 (1994)] and are shown in Table 1. Asdescribed in that article, high selectivities to cyclohexylbenzenerelative to BP during the desulfurization reaction are a good indicationof a catalyst with high hydrodenitrogenation activity, whereas highselectivities of BP relative to CHB indicates a catalyst with highhydrodesulfurization activity.

The results show that partial substitution of tungsten for molybdenumresults in catalysts that are substantially higher for DBT conversion. Astandard supported Ni—Mo on Al₂O₃ catalyst is also shown for comparison.The high CHB/BP ratio suggests that the catalysts are active for HDN.

TABLE 1 Comparison of Activity in DBT Conversion Tests With TungstenAddition by Different Preparation Schemes CHB/ preparation exampleK_(total) @ BP @ catalyst technique # 350° C. 350° C. NH₄—Ni—Mo—Oboiling 1 106 10.4 decomposition NH₄—Ni—Mo_(.5)W_(.5)—O boiling 2 17110.2 decomposition NH₄—Ni—Mo_(.5)W_(.5)—O direct 3 167 12.4precipitation NH₄—Ni—Mo_(.5)W_(.5)—O controlled PH 4 181 12.0preparation Ni,Mo/Al₂O₃ impregnation 129 6.4

EXAMPLE 6

A series of catalysts were prepared in accordance with the generalpreparation scheme of example 2 (i.e. boiling decomposition) but varyingthe Mo and W relative ratios by changing the amount of ammoniummolybdate and ammonium metatungstate added to the solutions.Decomposition was effected as described in Example 5. The catalysts soprepared are shown in Table 2 alone with their catalytic activities forDBT measured as described in Example 5.

TABLE 2 Comparison of Activity in DBT Conversion Tests with Variation inRelative W and Mo content ammonium ammonium nickel nitrate K_(total)CHB/BP molybdate metatungstate hexahydrate @ @ Catalyst Sample (g) (g)(g) 350° C. 350° C. NH₄—NiW—O 18983-97 0 36.95 43.62 128 11.3NH₄—NiMo_(.1)W_(.9)—O 18983-125 2.65 33.62 43.62 132 14.1NH₄—NiMo_(.3)W_(.7)—O 18983-101 7.94 25.87 43.62 154 11.6NH₄—NiMo_(.5)W_(.5)—O 18357-109 13.17 18.74 43.62 171 10.2NH₄—NiMo_(.7)W_(.3)—O 18983-95 18.54 11.09 43.62 158 11.5NH₄—NiMo_(.9)W_(.1)—O 18983-92 23.83 3.69 43.62 141 10.5

The data show that the most active catalyst contains an approximatelyequimolar mixtre of tunsten and molybdenum.

EXAMPLE 7

A series of catalysts were prepared as described in Example 3 (directprecipitation) in which equimolar mixtures of Mo and W were precipitatedbut the nickel content was varied. Decomposition was effected asdescribed in Example 5. The casalysts so prepared are shown in Table 3along with their catalytic activities for DBT measured as described inexample 5.

TABLE 3 Variation of Nickel Content in NH₄—Ni—Mo_(.5)W_(.5)—O Catalystsammonium ammonium nickel nitrate K_(total) CHB/BP molybdatemetatungstate hexahydrate @ @ Catalyst Sample (g) (g) (g) 350° C. 350°C. NH₄—Ni_(0.75)Mo_(.5)W_(.5)—O 19086-110 17.65 24.6 43.65 171 13.0NH₄—Ni_(1.0)Mo_(.5)W_(.5)—O 19086-82 17.65 24.6 58.2 167 12.4NH₄—Ni_(1.25)Mo_(.5)W_(.5)—O 19086-111 17.65 24.6 72.75 174 11.0NH₄—Ni_(1.5)Mo_(.5)W_(.5)—O 19086-112 17.65 24.6 87.3 148 9.55

Catalytic performance does not change substantially with variations inNi from 0.75 to 1.5, although K appears to go through a maximum at about1.25 Ni.

EXAMPLE 8

A series of catalysts were prepared in which the quantity of NH₄OH usedin the preparation was varied. The catalysts were prepared in accordanceto the procedure described in Example 3 except that the amount of NH4OHin solution A was varied to change to NH₄OH/Ni molar ratio when the twosolutions were mixed. Decomposition was effected as described in Example5. The catalysts so prepared are shown in Table 4 along with theircatalytic activities for DBT measured as described in Example 5.

TABLE 4 Variation in NH₄OH Addition to Preparation Catalyst ammoniumammonium nickel nitrate cm³ K_(total) K_(CHB)/ NH₄OH/Ni molybdatemetatungstate hexahydrate conc (@) BP (@) mole ratio Sample (g) (g) (g)NH₄OH 350° C. 350° C. 1:2 19086-96 17.65 24.6 43.65 6.8 102 10.5 1:119086-97 17.65 24.6 58.2 14 137 10.4 2:1 19086-82 17.65 24.6 72.75 30167 12.4 3:1 19086-104 17.65 24.6 87.3 41 164 11.4 4:1 19086-106 17.6524.6 87.3 55 161 12.1

While decomposition of the precursor compound will drive off most, ifnot all, of the ammonium portion of the precursor, the preparation ofthe precursor and the catalytic utility of the decomposition product canbe affected by the amount of NH₄OH employed. Thus, the effectiveness ofthe decomposition product as a catalyst is enhanced when the NH₄OH/Niratio in the preparation of the precursor compound is from about 1:1 toabout 4:1, preferably about 1.5:1 to about 4:1, and more preferablyabout 2:1 to about 4:1. While not wishing to be bound by any particulartheory or mechanism, there is some evidence the NH₄OH/Ni ratio causesthe Ni—M—W—O phase to change in the decomposition product.

EXAMPLE 9

The catalysts of examples 1 and 2 were compared against standardsupported Ni—Mo catalysts for the conversion of a LSADO (low sulfur autodiesel oil feed). This feed contained 510 wppm sulfur, 50 wppm nitrogen,and 30.6% aromatics with a gravity of 39.8° API. The catalysts weretested at 304° C. 650 psig of H₂, and 1850 SCFB/B of H₂). The relativeactivities of the different catalysts are summarized in Table 5.

TABLE 5 Relative Hydrotreating Activities on LSADO Feed RelativeVolumetric Relative Volumetric Catalyst HDS Activity HDN ActivityNi—Mo/Al₂O₃ 1 1 NH₄—NiMo—O 0.25 0.50 NH₄Ni_(1.0)Mo_(.5)W_(.5)—O 1.4 2.05

The Ni—Mo/Al₂O₃ catalyst is a standard HDN/HDS catalyst, the NHL—Ni—Mophase is the bulk phase with no tungsten, and theNH₄—Ni_(1.0)Mo_(.5)W_(.5)—O is the bulk phase with partial substitutionof W for Mo. The NH₄—NiMO—O catalyst is also representative of knowncompounds. The catalyst of this invention is illustrated byNH₄—Ni_(1.0)Mo_(0.5)W_(0.5)—O and the data show the clear advantage ofammonium nickel tungsten molybdate for HDN/HDS activity.

EXAMPLE 10

Preparation of a bulk catalyst composition according to the solid route:18.1 kg-ammonium dimolybdate (15.33 kg MoO₃) are dissolved in 575 literswater. Subsequently 28.5kg ammonium metatungstate (24 69kg WO₃) is addedto the solution. The resulting solution is preheated up to 90° C.26.5kgNiCO₃ (49.7% Ni) powder is mixed with water and the resulting paste isadded to the ammonium dimolybdate/ammonium metatungstate solution. Theresulting mixture is reacted for 7 hours at 89° C.

EXAMPLE 11

Preparation of a bulk catalyst composition according to the solutionroute: In a 1-liter flask, 13.2 g ammonium molybdate (0.075 moles Mo),18.7 g ammonium metatungstate (0.075 moles W) and 43.6 g nickel nitratehexahydrate (0.15 moles Ni) were dissolved in 300 ml water so that theresulting pH equaled 4.3. To this solution, a concentrated NH4OHsolution (about 600 ml) was added until the pH reached 10. At thispoint, some precipitate remained. The solution was refluxed at 100° C.for 3 hours. During this heating, the precipitate dissolved to give aclear blue solution and on further heating, a green precipitate formed.The heating was continued until the pH reached a value between 6.8 and7.0. The suspension was cooled to room temperature, filtered, washedwith water and dried at 120° C. overnight. 18 grams of material wereobtained.

EXAMPLE 12 (Sample 2110587)

657g of a NiMo—W bulk catalyst composition obtained according to theprocedure described in Example 10 was added to 1362 g of an aqueousslurry containing 125g of alumina (prepared by precipitation of sodiumaluminate and aluminum sulfate). The resulting Ni—Mo—W bulkcatalyst-alumina composition was subsequently mixed at 80° C. until anLOI of 31% was obtained. The resulting composition was subsequentlyextruded and the extrudates were dried at 120 C. for about 90 minutesand subsequently calcined at 385° C. for one hour in air.

EXAMPLE 13 (Sample 2110598)

The process of Example 10 was repeated except that instead of thealumina suspension, a silica sol containing 10 wt. % silica wereapplied.

EXAMPLE 14 (Sample 2110591)

657g of a Ni—Mo—W bulk catalyst composition obtained according to theprocedure described in Example 10 was added to 510 g of a boehmite pastecontaining 125g boehmite. The rebuffing paste was mixed at 60° C. toobtain an LOI of 42%. The resulting composition was extruded, dried andcalcined as described in Example 12.

EXAMPLE 15 (Sample 2110469)

The procedure described in Example 10 was repeated except that aluminais present during the preparation of the bulk catalyst composition. To755g of the resulting dried Ni—Mo—W bulk catalyst-alumina compositioncontaining 60g alumina, 461g water and a small amount of nitric acidwere added. The resulting mixture was mixed at 70° C. while evaporatingwater until an LOI of 34% was obtained. The resulting composition wasextruded, dried and calcined as described in Example 12.

EXAMPLE 16

Ammonium molybdate, ammonium tungsten and/or ammonium chromate aredissolved and combined in a first reactor. The temperature is increasedto 90° C. The Group VIII salt is dissolved in a second reactor andheated to 90° C. Ammonium hydroxide is added to the first reactor toform a basic solution. The Group VIII metal solution is added to thefirst dropwise with stirring in 20 minutes. After 30 minutes, theprecipitate is filtered and washed. The precipitate is dried overnightat 120° C. and calcined at 385° C.

EXAMPLE 17

The precipitation method of Example 16 was used to prepare a precipitatefrom ammonium dimolybdate, ammonium meta tungstate andFe(III(NO₃)_(3·)9H₂O in 98% yield comprising 41.2 wt. % Fe₂O_(3,) 21.3wt. % MoO₃, and 36.9 wt. % WO₃. The surface area of the precipitate was76 m²/g. The pore volume as measured up to 60 mn by BET using theadsorption curve was 0.147 ml/g.

EXAMPLE 18

The precipitation method of Example 16 was used to prepare a precipitatefrom Ni(CO₃)_(2·)6H₂O,(NH₄)₆Mo₇O_(24·)4H₂O, and (NH₄)₂Cr₂O₇ in 87.7%yield comprising 52.2 wt. % NiO, 29.4 wt. % MoO_(3,) and 16.6 wt. %Cr₂0₃. The surface area of the precipitate was 199 m²/g. The pore volumeas measured up to 60 nm by BET using the adsorption curve was 0.276ml/g.

EXAMPLE 19

The precipitation method of Example 16 was used to prepare a precipitatefrom Ni(CO₃)_(2·)6H₂O, (NH₄)₆H₂W₁₂O₄₀, and (NH₄)₂Cr₂O₇ in 87.7% yieldcomprising 44.0 wt. % NiO, 42.4 wt. % WO₃, and 11.8 wt. % Cr₂O₃. Thesurface area of the precipitate was 199 m²/g. The pore volune asmeasured up to 60 nm by BET using the adsorption curve was 0.245 ml/g.

Hydrotreating Raw Virgin Petroleum Distillates

The activity advantage and she strong pressure response of bulkmultimetallic Ni—Mo—W catalysts of the present invention, referred toherein as “BMCat,” over conventional bimetallic Group VIIIEGroup VIBbimetallic hydrotreating catalysts for HDS and HDN is demonstrated belowthrough hydrotreating of a European raw virgin feed, raw virgindistillate designated FS-9593. Comparison between the activity of theBMCat and a conventional supported CoMo on alumina/silica catalyst,commercially available as KF756 from Akzo Nobel, has been obtainedbetween 150 and 400 psig. Selected feedstock properties are listed inTable 6. Results are found in Tables 7, 8 and 9.

TABLE 6 Analytical Summary for 100% Virgin Distillate (FS-9593) TestName Result(s) Sulfur in Oils 9320 wppm Nitrogen by Antek  79 wppmGravity 35.4° API GCD D-2887  5.0 wt. % 398° F. (203° C.) 50.0 wt. %561° F. (294° C.) 95.0 wt. % 656° F. (347° C.)

EXAMPLE 20

A reactor was charged with 6 cc of a Co substituted BMCat(Co_(0.3)Ni_(1.2)Mo_(0.5)Wo_(0.5)) which was diluted to 8 cc usingdenstone. After liquid phase sulfiding the catalyst was used to processa raw virgin distillate (Table 6) in a pressure range of 150-400 psig.The lineout liquid products were analyzed for sulfur by X-ray and fornitrogen by Antek Comparison of Example 20 with Example 23 reveals thatthe bulk trimetallic catalyst of the present invention has a muchstronger pressure response than the conventional bimetallic KF756catalyst.

EXAMPLE 21

The procedure of Example 20 was repeated except that the cobalt level ofthe BMCat was 0.4 wt. % instead of 0.3 wt. %. Comparison of Example 21with Example 23 again reveals that the BMCat of the present inventionhave much stronger pressure response than the conventional bimetallicKF756 catalyst.

EXAMPLE 22

The procedure of Example 20 was repeated except that the 0.75 wt. % Cowas used instead of 0.3 wt. %. Comparison of Example 22 with Example 23again reveals that the BMCat of the present invention have much strongerpressure response than the conventional bimetallic KF756 catalyst.

EXAMPLE 23 (COMPARATIVE)

The procedure of Example 20 was repeated except that only theconventional bimetallic KF756 catalyst comprised of CoMo/Al₂O₃ wascharged in the reactor. Comparison of Example 23 with Example 20, 21 and22 reveals that the BMCat of the present invention have much strongerpressure response than the conventional bimetallic KF756 catalyst.

TABLE 7 Comparison of KF756 and BMCats at 150 psig. Virgin Distillate(FS- 9593) (S = 9320 ppm, N = 79 ppm). 330° C., 150 psig, 1.0 LHSV, TGR= 2000 SCF/B. Product S⁽¹⁾ 1.5-order HDS RVA to Product N⁽³⁾ HDN RVA ppmκ_(HDS) ⁽²⁾ RT-601 ppm to KF756 Example 23 κF756 177(8) 6.5 100 53(3)100 Example 24 BMCat 210(2) 5.8 89 39(2) 175 Example 20 Co0.3 BMCat251(18) 5.3 82 39(5) 175 Example 21 Co0.4 BMCat 336(4) 4.1 63 46(2) 130Example 22 Co0.75 BMCat 376(14) 4.4 68 47(4) 125 ⁽¹⁾The value inparentheses is the standard deviation. Product sulfers are averages of afew balances after activity lineout. ⁽²⁾κ_(HDS) = LHSV*(1/SQRT[S] -1/SQRT[S]₀)*100. ⁽³⁾The value in parentheses is the standard deviation.Product nitrogens are not lined out values.

TABLE 8 Comparison of BMCats with KF756 for HDS and HDN at DifferentProcess Pressures. Virgin Distillate (FS-9593) (S = 9320 ppm, N = 79ppm). 330° C., 1.0 LHSV, TGR = 2000 SCF/B. HDS Relative to KF756⁽¹⁾ HDNRelative to KF756⁽²⁾ H₂ Pressure, psig 150 250⁽³⁾ 400 150 250⁽³⁾ 400Example 20 Co0.3-BMCat 81 130 300 170 350 432 Example 21 Co0.4-BMCat 6893 200 162 230 380 Example 22 Co0.75-BMCat 63 98 200 125 325 400 Example23 BMCat (powder) 89 — — 175 — — ⁽¹⁾1.5-order volumetric rate constants.⁽²⁾1st-order volumetric rate constants. ⁽³⁾Based on the data prior tolineout.

EXAMPLE 24

A reactor was charged with 6 cc of a BMCat having a compositionNi_(1.5)Mo_(0.5)W_(0.5) (this is the base composition for the bulkmultimetallic catalysts used in these examples where there no cobaltsubstitution) which was diluted to 8 cc using denstone. After liquidphase sulfiding the catalyst was used to process raw virgin distillate(FS-9593, Table 6) at a pressure of 150 psig. The lineout liquidproducts were analyzed for sulfur by X-ray and for nitrogen by Antek.The results were presented in Table 7 and 8 for comparison with KF756and other BMCats. Plots (FIGS. 3 and 4) of HDS and HDN activities versesreator hydrogen pressure provide a performance projection of BMCats ofthe present invention at mnoderate hydrogen pressure.

What is claimed is:
 1. A hydroprocessing process, comprising: contactinga feedstock, at hydrotreating conditions, with a bulk multimetalliccatalyst represented by the formula: (X)_(b)(Mo)_(c)(W)_(d)O_(z.)wherein X is a Group VIII non-noble metal, and the molar ratio of b:(c+d) is 0.5/1 to 3/1.
 2. The process of claim 1 wherein the Group VIIInon-noble metal is at least one of Ni and Co.
 3. The process of claim 1wherein the ratio of Mo to W is from about 9:1 to about 1:9.
 4. Theprocess of claim 1, wherein said molar ratio of b:(c+d) is 0.75/1 to1.5/1.
 5. The process of claim 1 wherein said molar ratio of c:dis >0.01/1.
 6. The process of claim 1 further comprising sulfiding amultimetallic oxide precursor to form said bulk multimetallic catalyst,wherein the precursor comprises essentially an amorphous material havinga unique X-ray diffraction pattern showing crystalline peaks at d=2.53Angstroms and D=1.70 Angstroms.
 7. The process of claim 1 wherein saidfeedstock comprises at least one of naphtha, diesel, heavy gas oil, lubeoil, and residuum virgin distillates.
 8. The process of claim 1 whereinsaid feedstock comprises naphtha boiling in the range of 25° C. to 210°C., and said hydrotreating conditions include a reaction temperature of100° C. to 370° C., a pressure of 10 Bar to 60 Bar, a space velocity of0.5 to 10 V/VHr, and a hydrogen gas treat rate of 100 to 2,000 SCF/B. 9.The process of claim 1 wherein said feedstock comprises diesel boilingin the range of 170° C. to 350° C., and said hydrotreating conditionsinclude a reaction temperature of 200° C. to 400° C., a pressure of 15Bar to 110 Bar, a space velocity of 0.5 V/V/Hr to 4 V/V/Hr, and ahydrogen gas treat rate of 500 SCF/B to 6,000 SCF/B.
 10. The process ofclaim 1 wherein said feedstock comprises heavy gas oil boiling in therange of 325° C. to 475° C., and wherein said hydrotreating conditionsinclude a reaction temperature of 260° C. to 430° C., a pressure of 15Bar to 170 Bar, a space velocity of 0.3 V/V/Hr to 2 V/V/Hr, and ahydrogen gas treat rate of 1,000 SCF/B to 6,000 SCF/B.
 11. The processof claim 1 wherein said feedstock comprises a lubricating oil boiling inthe range of 290° C. to 550° C., and wherein said hydrotreatingconditions include a reaction temperature of 200° C. to 450° C., apressure of 6 Bar to 210 Bar, a space velocity of 0.2 V/V/Hr to 5V/V/Hr, and a hydrogen gas treat rate of 100 SCF/B to 10,000 SCF/B. 12.The process of claim 1 wherein said feedstock comprises a residuumhaving a 10% to 50% boiling range of 575° C., and wherein saidhydrotreating conditions include a reaction temperature of 340° C. to450° C., a pressure of 65 Bar to 1100 Bar, a space velocity of 0.1V/V/Hr to 1 V/V/Hr, and a hydrogen gas treat rate of 2,000 SCF/B to10,000 SCF/B.
 13. The process of claim 1 wherein the bulk multi-metalliccatalyst comprises particles having a median diameter of at least 50 nm,a surface area of at least 10 m²/gm, a pore volume ranging from 0.05 to5 ml/g, and an absence of pores small than 1 nm.
 14. The process ofclaim 13 wherein said bulk multimetallic catalyst particle comprises acore-shell structure.
 15. The process of claim 1 further comprisingcontacting at least one of said feedstock and hydroprocessed productwith a catalytically effective amount of a second catalyst undercatalytic conversion conditions.
 16. The process of claim 15 whereinsaid second catalyst comprises at least one of a hydroprocessingcatalyst, a cracking catalyst, and an isomerization catalyst.
 17. Theprocess of claim 16 wherein said second catalyst is present in at leastone of a first reaction zone or zones upstream of said bulkmultimetallic catalyst; a second reaction zone or zones containing saidbulk multimetallic catalyst; and a third reaction zone or zonesdownstream of said bulk multimetallic catalyst.
 18. The process of claim1 wherein said bulk multimetallic catalyst is a sulfided catalyst. 19.The process of claim 1 wherein said bulk multimetallic catalyst issulfided in-situ.